Effect of annealing treatment on hydrogen storage properties of La-Ti-Mg-Ni-based alloy

The present study dealt with investigations on the effects of annealing on the hydrogen storage properties of La 1.6 Ti 0.4 MgNi 9 alloys.The experimental alloys were prepared by magnetic levitation melting followed by annealing treatment.For La 1.6 Ti 0.4 MgNi 9 alloys,LaNi 5,LaNi 3 and LaMg 2 Ni 9 were the main phases,Ti 2 Ni phase appeared at 900℃.Annealing not only enhanced the maximum and effective hydrogen storage capacity,improved the hydrogen absorption/desorption kinetics,but also increased the discharge capacity.The cyclic stability had been improved markedly by annealing,e.g.,when the discharge capacity reduced to 60% of maximum discharge capacity,the charge/discharge cycles increased from 66(as-cast) to 89(annealed at 800℃) and 127 times(annealed at 900℃).La 1.6 Ti 0.4 MgNi 9 alloy annealed at 900℃ exhibited better electrochemical properties compared to the other two alloy electrodes.     

La1＋xMg2-xNi9（x=0，0．5，1．0，1．5）合金的储氢性能及电化学性能研究

利用高频熔炼方法制备了La1＋xMg2-xNi9（x=0，0．5，1．0，1．5）系列合金，并对其进行了XRD分析和储氢容量及电化学性能测定。结果表明：随着La含量增大，合金中LaNi5和（La，Mg）Ni3相转变为LaNi3相，且Mg2Ni相出现，晶胞体积也增大，合金的储氢容量和电化学性能提高；当x=1．5时，Mg2Ni相消失，合金的储氢性能有所下降。当x=1．0时，即La2MgNi9合金具有较好的储氢容量及电化学容量。     

铸态及退火La1.9Ti0.1MgNi9合金的贮氢性能

采用磁悬浮感应熔炼及退火处理的方法,制备La1.9Ti0.1MgNi9合金。对合金样品的XRD、PCT和电化学测试表明,所有样品均由多相组成,LaNi5相为主相。当退火温度达到1173 K时,合金中LaMg2Ni9相消失,Ti2Ni相出现。退火处理能提高合金的晶化程度、降低吸放氢平台压。退火1073 K合金的有效吸氢量较高,在303 K时达到1.25% (质量分数)。La1.9Ti0.1MgNi9合金退火后,放电容量、循环稳定性以及高倍率放电性能得到极大改善,以1173 K退火合金电化学性能较好,其最大放电容量为377 mAh/g,1100 mA/g电流密度下的高倍率放电性能为0.839,经112次充放电循环后放电容量保持率为60%。     

B对Mg76-xTi12Fe8Ni4Bx (x=0, 1, 2, 3, 4)合金储氢性能的影响

利用机械合金化方法制备了Mg76-xTi12FesNi4Bx(x=0,1,2,3,4)合金并对其储氢性能进行了系统的研究.在Mg76-xTi12FesNi4Bx(x=0,1,2,3,4)合金中,Mg2Ni和NiTi是主要的合金相.B的加入使合金的非晶化程度提高,也降低了合金的吸放氢温度和滞后效应,但吸放氢平台有所上升,合金的吸氢量以及吸放氢速率均有下降.     

Effect of AB2-based alloy addition on structure and electrochemical properties of La0.5Pr0.2Zr0.1Mg0.2Ni2.75Co0.45Fe0.1Al0.2 hydrogen storage alloy

The La 0.5Pr0.2Zr0.1Mg0.2Ni2.75Co0.45Fe0.1Al0.2(M1) and Zr0.65Ti0.35(Mn0.2V0.2Cr0.15Ni0.45) 1.76(M2) hydrogen storage alloys were prepared by inductive melting.In addition,the M1+30 wt.%M2 composites were successively prepared by using high-energy ball milling technology.From the X-ray diffraction(XRD) analysis,it was found that M1 and M2 alloys still retained their respective main phases in the M1+30 wt.%M2 composites.The scanning electron microscopy(SEM) and energy dispersive spectroscopy(EDS) indicated that the decrease in discharge capacity of M1 and M2 alloy electrodes was ascribed to the oxidation-dissolution of La,Pr,Mg and Ti,Mn,V,Cr active elements,respectively.The electrochemical studies showed that the M1+30 wt.%M 2 composite electrode ball milling for 5 min exhibited excellence cyclic stability(92.3%) after 80 charge/discharge cycles,which was higher than 77.7 % and 85.6% of M1 and M2 alloy electrodes,respectively.Moreover,at the discharge current density of 1200 mA/g,the high rate discharge ability(HRD) of the M1+30 wt.%M2 composite electrode increased from 61.5%(5 min) to 70.3%(10 min).According to the linear polarization,Tafel polarization and cyclic voltammograms(CV),the electrochemical kinetics of hydrogen reaction on the surface of the electrode and hydrogen diffusion rate in the bulk of alloy were also improved in the M1+30 wt.%M2 composite with increasing ball milling time.     

Fe、Co和Ni掺杂LiBH4放氢性能的第一性原理研究

本工作旨在借助基于密度泛函理论的第一性原理计算来考察过渡金属元素Fe、Co、Ni掺杂LiBH_4的放氢性能。研究表明,Fe、Co、Ni掺杂有效提高了LiBH_4的放氢能力,这与掺杂体系B-H共价作用及Li-B/H离子作用的减弱,尤其是Fe/Co/Ni-B键的形成有关。体系Li7MB8H_32(M=Li、Fe、Co、Ni)的氢解离能与中心金属M的电负性负相关,即金属M的电负性越高,体系的氢解离能越小。与Fe、Co掺杂体系相比,具有较低金属占位能及较小氢解离能的Ni掺杂体系表现出良好的放氢特性。本研究从模拟计算的角度证实,利用高电负性金属(相对Li)与LiBH_4复合是实现LiBH_4"失稳"的一种有效方式。     

二元合金Laves相结构的PLS分析

运用模式识别的偏最小二乘法(PLS)对AB2合金MgCu2型(C15)和MgZn2型(C14)Laves相进行研究,得出了影响二元合金Laves相结构的判据．对于由非过渡一过渡元素、过渡一过渡元素组成的合金,价电子密度是影响其Laves相结构的主要原因;对过渡一镧系(锕系)元素组成的合金,B原子的价电子数对其Laves相结构影响最为明显,且价电子和原子半径对Laves相结构的影响作用互为反向．     

Hydrogen Storage Properties of Co-free La-Mg-Ni-Based Alloys

在Ar气保护下采用磁悬浮感应熔炼方法,制备无CoLa1.8Ti0.2MgNi9-xAlx(x=0,0.1,0.2,0.3,0.4)合金,系统研究Al取代Ni对合金的结构及贮氢性能的影响。所有合金均包含LaMg2Ni9相,当Al含量x≥0.1,La(Ni,Al)5相取代LaNi5相、LaNi3相消失、LaNi2相出现。测试合金的焓变值与LaNi5合金(–30.6kJ/molH2)相近。Al取代Ni不仅提高合金电极的放电容量,而且改善循环稳定性及电化学动力学性能。La1.8Ti0.2MgNi8.7Al0.3合金贮氢性能较好,30℃下有效吸氢质量分数为1.32%;最大放电容量达到340mAh/g;1400mA/g放电电流密度下高倍率放电性能HRD1400高达79.8%;经100次充放电循环放电容量保持率为60%。